HUT54333A - Process and catalyst for producing ethylene and acetic acid - Google Patents

Abstract

A process and catalyst for the production of ethylene and/or acetic acid by oxidation of ethane and/or ethylene with a molecular oxygen-containing gas in the presence of a catalyst composition comprising the elements A, X and Y in combination with oxygen, the gram-atom ratios of the elements A:X:Y being a:b:c, wherein A = ModReeWf; X = Cr, Mn, Nb, Ta, Ti, V and/or W; Y = Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U; a = 1; b = 0 to 2; c = 0 to 2; d + e + f = a; d is either zero or greater than zero; e is greater than zero; and f is either zero or greater than zero.

Description

Great Britain

The present invention relates to a process for the preparation of ethylene and acetic acid and to a catalyst used in the process.

Catalytic dehydrogenation of ethane is described in several patents, such as U.S. Patent Nos. 4,250,346, 4,524,236 and 4,568,790, and European Patent Nos. 0,294,845.

U.S. Patent No. 4,250,346 discloses the oxidative dehydrogenation of ethane to ethylene in which the gas phase reaction provides relatively high conversion, selectivity and productivity, the reaction temperature is lower than 500 ° C, and a catalyst composition is used which contains molybdenum X. It consists of Y and Y elements and has the following general formula:

Mo X. Y a b in which

X is selected from chromium, manganese, niobium, thallium, titanium, vanadium and / or tungsten, preferably manganese, niobium, vanadium and / or tungsten;

Y is bismuth, cerium, cobalt, iron, potassium, magnesium, nickel, phosphorus, tin, antimony, silicon, tantalum and or uranium, preferably antimony, cerium and / or uranium;

a is 1;

between 0.05 and 1.0; and φ

0 to 2, preferably 0.05 to 1.0, with the proviso that the total value of c for cobalt, nickel and / or iron may not exceed 0.5.

In the process described in U.S. Patent No. 4,524,236, an oxidehydrogenation of ethane to ethylene is carried out using an annealed catalyst Q □ C0 6 Mo V.NbSb Λ.

U.S. Patent 4,568,790 discloses a process wherein the low temperature catalytic oxide hydrogenation of ethane to ethylene is accomplished by a gas phase process and using a Mo,, Nb Sb, DC3 catalyst, wherein 5 to 0.9;

b is from 0.1 to 0.4;

between 0.001 and 0.2;

d is 0.001-0.1.

Although the patents described above mention the formation of acetic by-product, these processes are primarily concerned with the production of ethylene.

However, in the process disclosed in the recently published patent application EP-A-0 294 845, the primary purpose is the production of acetic acid.

In the process described in EP-A-0 294 845, the selective preparation of acetic acid is carried out by reacting ethane, ethylene or a mixture of ethane and ethylene with oxygen in the presence of a catalyst which:

A is a glowed ethane oxidation catalyst containing molybdenum, vanadium, and optionally at least one other metal atom, and is characterized by a general Mo V x y in which the metallic elements are present in the form of various oxides; and

B / contains an ethylene hydrogenation and / or ethylene oxidation catalyst. Z optionally present in the above general formula may be one or more of lithium, sodium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, hyium, paste, scandium, yttrium, lanthanum. -, cerium, aluminum, thallium, titanium, zirconium, hafnium, lead, niobium, tantalum, arsenic, antimony, bismuth, chromium, tungsten, uranium, tellurium, iron, cobalt and nickel, and x is 0.5-0.9, y is 0.1-0.4, and z is 0-1.

None of the above patents mention the use of a rhenium catalyst component, although U.S. Pat.

We have now found that the molybdenum component of the oxidative dehydrogenation catalyst described above can be replaced in whole or in part by rhenium or by a combination of rhenium and tungsten, and the composition of the product formed depends on the degree and nature of the molybdenum substitution. For example, the replacement of all molybdenum with rhenium may substantially eliminate acetic acid formation, while partial replacement of molybdenum with rhenium may increase the selectivity of acetic acid formation.

The present invention relates to a process for the preparation of a product containing ethylene and / or acetic acid from ethane gas and / or ethylene gas, wherein the gas containing ethane and / or ethylene and molecular oxygen is contacted at an elevated temperature with oxidized dehydrogenation catalyst Rhenium or a combination of rhenium and tungsten.

The present invention also relates to a molybdenum-containing ethane oxidative dehydrogenation catalyst composition wherein the molybdenum is wholly or partially replaced by rhenium or a combination of rhenium and tungsten.

In such catalyst compositions, A, X, and Y are present together with oxygen, and the grams of A, X, and Y are a: b: c, respectively.

In the catalyst composition, the

Component A is represented by the general formula Mo ^ re and is

X is a chromium, manganese, niobium, tantalum, titanium, vanadium, and / or tungsten atom, preferably a manganese, niobium, vanadium, and / or tungsten atom;

Y is bismuth, cerium, cobalt, copper, iron, potassium, magnesium, nickel, phosphorus, lead, antimony, silicon, tin-thallium and / or uranium and preferably tin -, cerium and / or uranium;

the is 1; b 0-2, preferably 0.05-1.0; c 0-2, preferably 0.001-1.0, more preferably

0.05 to 1.0, with the proviso that the total value of c for cobalt, nickel / iron atoms may not exceed 0.5;

d + e + f = a;

d is 0 or more;

e is greater than 0; and f is a number greater than or equal to 0.

In preferred catalyst compositions, the A, niobium, antimony and Z elements are present together with oxygen and the gram ratio of A, niobium, antimony and Z elements is respectively: a: b: c: g and

A has the same meaning as defined above;

Z is at least one calcium, ruthenium or gallium atom, preferably calcium;

a, b and c are as defined above; and g is 0 to 2, preferably greater than 0.

In more preferred catalyst compositions, the A, vanadium, niobium, antimony and Z elements are present together with oxygen and the gram ratio of A, vanadium, niobium, antimony and Z elements is respectively: h: b c: g; and that

A and Z have the same meanings as defined above;

a, b, c and g are as defined above; and h is from 0 to 1.0.

Typical examples of catalyst compositions useful in the process of the present invention include:

^Mo 0.56 ^Re 0.0h ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 (III) ^Mo 0.37 ^Re 0.25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 (ARC) ^W, 0.37 R s 0.25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 (V) ^M ° 0.24 Re ^re 0.37 ^V 0.26 ^Nb 0.07 ^Sb 0.04 ^Ca 0.02 and (VI) ^Re 0.61 ^V 0.26 ^Nb 0.07 ^Ca 0.02 ^Sb 0.04 (VII)

It should be noted that the elements are present in the formulations together with oxygen.

By using molybdenum-containing catalysts of formula (III / -) / VI, acetic acid can be prepared from ethane as described above. The selectivity of the catalysts is generally higher than that of the oxidative dehydrogenation catalysts reported so far. Alternatively, if the catalyst (VII) containing wholly rhenium is used instead of molybdenum, ethylene can be prepared from ethane essentially free of acetic acid.

The catalyst compositions of the present invention may be prepared by any conventional method. The preparation can take place from solutions and / or complexes and / or compounds of soluble compounds of metals. The solutions are preferably aqueous systems having a pH in the range of 1 to 12, preferably 2 to 8, and a temperature of 20 to 100 ° C.

Generally, a mixture of elemental compounds is prepared by dissolving a sufficient amount of the soluble compounds, and then dispersing any insoluble compound that may be used in the solution to obtain the desired gram ratio of the catalyst composition components. The catalyst composition is obtained by removing the solvent from the mixture. The catalyst composition is then annealed. The annealing is carried out at 200-550 ° C in the presence of air or oxygen for 1 minute to 24 hours. The air or oxygen is preferably supplied slowly.

The catalyst may be supported or un supported.

Suitable carriers include silica, alumina, zirconia, titanium dioxide, silicon carbide and mixtures of two or more of these.

Further details on catalyst preparation can be found, for example, in EP-A-0 166 438.

The catalyst may be applied in a fixed or fluidized bed.

Ethane and / or ethylene, preferably ethane, may be used as feed gas. Ethane forms ethylene and optionally acetic acid, and ethylene forms acetic acid.

Ethane and / or ethylene may be used in substantially pure form or may be used in combination with one or more components of nitrogen, methane, carbon dioxide and water vapor components used in relatively high amounts, e.g. hydrogen, carbon dioxide, C3-C4 alkene, and alkene components.

The molecular oxygen-containing gas may be air or a gas containing less or more oxygen than the oxygen content of the air, such as oxygen. Such a gas may be, for example, oxygen diluted with a suitable amount of a diluent, such as nitrogen.

• «

In addition to the feed of ethane and / or ethylene and the molecular oxygen gas, water / steam / feed that improves the selectivity of acetic acid formation is preferred.

The elevated temperature is from 200 ° C to 500 ° C, preferably from 200 ° C to 400 ° C.

The process is carried out at atmospheric pressure or higher, for example 0.1 to 5.0 MPa, preferably 0.1 to 3.0 MPa.

Information on operating conditions and other information useful in the process of the present invention can be found in the literature, for example, in U.S. Patent No. 4,250,346.

The following examples illustrate the process of the invention in more detail. The terms used in the examples have the following meanings:

GHSV = Gas Hourly Space Velocity per hour = volume of gas flowing through the catalyst bed fml / hr / volume of catalyst bed [ml.J

Ethane Conversion = 100x [00 ^ / 2 + (002 ^ / 2 + ^ 2 ^ 4)

ECO] / ₂ ⁺ E 2 ° 2 ^ ^Z 2 ⁺ [ ^C 2 ^{H a J +} [ ^c 2 ^{H a} ] ⁺ [ ^CH 3 ^{C 00 H} ] Ethylene Selectivity £%] = 100 χ [, ^ 2 ^Η 4 ^ [CO] / _{2 +} [CO ₂ J / ₂₊ [C ₂ H ₄ J ₊ [cHjCOOHj

Acetic acid selectivity [%} = 100 x [CH.COOHj [coj / ₂₊ [co ₂ ] / ₂ * [c ₂ Hj ₊ [; ch ₃ cooh]

- 10 where t] = concentrations in mole%, [c ₂ h ₆ ] = concentration of unmodified ethane

Catalyst preparation:

In the examples, the composition of the catalyst compositions is expressed in relative grams of the elements, but these elements are present together with oxygen.

Preparation of catalyst A / 111:

A catalyst having the following composition was prepared:

^Mo 0.56 ^Re 0.06 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02

The preparation was carried out by adding 7.4 g of ammonium metavanadate to 80 ml of water and heating with stirring at 70 ° C for 15 minutes. The other solution was prepared by adding a mixture of 4.7 g of niobium pentachloride, 1.6 g of antimony trichloride, 1.0 g of calcium nitrate and 4.0 g of ammonium perrenate to 40 ml of water. 7.5 g of oxalic acid dissolved in ml of water and the resulting solution was stirred at 70 ° C for about 15 minutes. The first solution is combined with the second solution and the resulting solution is stirred at 70 ° C for 15 minutes. Dissolve 23.8 g of ammonium molybdenate in 80 ml of water and heat with stirring at 70 ° C for 15 minutes. This solution was then added to the combined first and second solutions, and the resulting mixture was heated at 70 ° C for 15 minutes. The resulting mixture is evaporated to dryness in a large evaporator bowl, hot water bath and hot air injection, *

- 11 fastest to remove. The solid thus obtained is dried for 16 hours at 110 ° C and then sieved to the appropriate particle size. The dry catalyst is annealed at 360 ° C for 3.5 hours. The annealing is carried out with air flow.

Preparation of catalyst A / IV:

A catalyst having the following composition was prepared:

^M ° 0.37 ^Re 0.25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02

The preparation was carried out by first adding 7.4 g of ammonium metavanadate to 80 ml of water and heating at 70 ° C for 15 minutes with stirring. The other solution was prepared by adding a mixture of 4.7 ml niobium pentachloride, 1.6 g antimony trichloride, 1.0 g calcium nitrate and 16.0 g ammonium perrenate to 40 ml water, and 40 ml 7.5 g of oxalic acid dissolved in water and the resulting solution is heated with stirring at 70 ° C for about 15 minutes. Combine the first solution with the second solution and heat the resulting solution at 70 ° C for 15 minutes. 15.9 g of ammonium molybdenate are dissolved in 80 ml of water and heated at 70 ° C for 15 minutes with stirring. This solution was then added to the combined first and second solutions and the resulting mixture was heated at 70 ° C for 15 minutes. The resulting mixture was evaporated to dryness, the solid was crushed and annealed as described above.

· »·· · * ··« <*

- Preparation of 12 catalysts of formula:

A catalyst having the following composition was prepared:

^W 0.37 ^Re 0.25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02

The preparation was performed by first adding 7.4 g of ammonium metavanadate to 80 ml of water and heating for 15 minutes with stirring. The other solution was prepared by adding a bed containing 4.7 g of niobium pentachloride, 1.6 g of antimony trichloride, 1.0 g of calcium nitrate and 16.0 g of ammonium perrenate to 40 ml of water, and Dissolve 7.5 g of oxalic acid in 40 ml of water and stir at 70 ° C for about 15 minutes. Combine the first solution with the second solution and heat the resulting solution at 70 ° C for 15 minutes. 23.5 g of ammonium tungstate are suspended in 60 ml of water and 52 ml of hydrogen peroxide are added with stirring, followed by heating at 70 ° C for 15 minutes. This solution was then added to the combined first and second solutions and the resulting mixture was heated at 70 ° C for 15 minutes. The resulting mixture was evaporated to dryness, the solid was crushed and annealed as described above.

Preparation of catalyst A / VI:

A catalyst having the following composition was prepared:

^M ° 0.24 ^Re 0.37 ^V 0.26 ^Nb 0.07 ^Sb 0.04 ^Ca 0.02

The preparation is carried out by first adding 25 ml of water

Ammonium metavanadate (1.7 g) was added and stirred at 70 ° C · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Μ ί ·· · · * * ♦ ·: · .. · .. ·

- Heat for 13 to 15 minutes. The other solution was prepared by adding a mixture containing 1.05 g of niobium pentachloride, 0.5 g of antimony trichloride, 0.3 g of calcium nitrate and 5.5 g of ammonium perrenate to 15 ml of water. 1.7 g of oxalic acid dissolved in water and the resulting solution was heated at 70 ° C with stirring for about 15 minutes. Combine the first solution with the second solution and heat the resulting solution at 70 ° C for 15 minutes. 2.4 g of ammonium molybdenate are dissolved in 25 ml of water with stirring and heated at 70 ° C for 15 minutes. This solution was then added to the combined first and second solutions and the resulting mixture was heated at 70 ° C for 15 minutes. The resulting mixture was evaporated to dryness, the solid was crushed and annealed as described above.

Preparation of catalyst A / VII:

A catalyst having the following composition was prepared:

^Re 0.61 ^V 0.2 H ^Nb 0.07 ^Ca 0.02 ^Sb 0.04

The preparation is carried out by first adding 40 ml of water

2.5 g of ammonium metavanadate are added and the mixture is heated at 70 ° C for one minute with stirring. The other solution was prepared by adding to a ml of water a mixture of 1.55 g of niobium pentachloride, 0.7 g of antimony trichloride and 0.4 g of calcium nitrate, followed by the addition of 3.7 g of oxalic acid in 20 ml of water, and heating the resulting solution with stirring at about 70 ° C for about 15 min. Combine the first solution with the second solution, · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·. ·· «· ·, ··· • · · · 9 aa • fc ·· a« ···

14 and the resulting solution was heated at 70 ° C for 15 minutes. 13.4 g of ammonium perrenate are dissolved in 100 ml of water with stirring and heated at 70 ° C for 15 minutes. This solution was then added to the combined first and second solutions, and the resulting mixture was heated at 70 ° C for 15 minutes. The resulting mixture was evaporated to dryness, the solid was crushed and then ash.

Preparation of catalyst A / VIII:

A catalyst having the following composition was prepared:

^Mo 0.37 ^Re 0.25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02

The preparation is carried out by first dissolving 10.0 g of ammonium perrenate and 9.7 g of ammonium molybdenate in 50 ml of water. The other solution was prepared by adding 4.5 g of ammonium metavanadate to 50 ml of water. The third solution was prepared by adding 10.2 g of niobium oxalate, 1.34 g of antimony oxalate and 0.58 g of calcium nitrate to 50 ml of water. The solutions were individually heated at 70 ° C with stirring for 15 minutes. The third solution is then added to the second solution. The combined solutions were heated with stirring at 70 ° C for 15 minutes, then added to the first solution and the resulting mixture was heated with stirring at 70 ° C for 15 minutes. The water is evaporated on a hot plate and the resulting thick paste is dried in an oven at 120 ° C overnight. The resulting solid was crushed and the 600-1200 µm fraction was separated by sieve and then incinerated for 5 hours at 300 ° C in standing air and then sieved to a diameter of 0.5-1.0 mm.

Preparation of catalyst A / IX:

A catalyst having the following composition was prepared:

^Mo 0.52 ^Re 0, l ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02

The preparation of the catalyst is carried out according to the procedure described for the preparation of the catalyst (VIII), using the desired relative amounts of ammonium perrenate and ammonium molybdenate.

Catalyst test:

Catalyst test procedure:

3 ml of catalyst was introduced into a stainless steel tubing of 5.6 mm internal diameter and placed in a tub furnace. The catalyst is then heated to 250 ° C with air at 5 ° C / min. Subsequently, a mixture of ethane, air, and nitrogen, which passes through a preheating zone maintained at 200 ° C and then through the catalyst, is fed through a plurality of trapped gas inlets. The reactor pressure is adjusted to the desired value with a pressure regulator and, if necessary, water is added to the preheating zone, where the water evaporates and mixes with the feed gas prior to contact with the catalyst. A sample of the vapor and gaseous product leaving the reactor is sampled and analyzed by gas-liquid chromatography (GLC). The temperature is measured with the thermocouple immersed in the catalyst bed.

GLC measurement conditions: gas analysis: 3 m Carbosieve S2 packed and molecular sieve column liquid analysis: 2.5 m CarboPack

B / Peg 20 M column.

Reaction conditions:

Reactor pressure: 1.4 MPa overpressure

GHSV: Approximately 3500 0 ^- ^

Nutrient composition: 21% by volume ethane, 3.8% by volume oxygen, 75.2% by volume nitrogen.

Reactor temperature: 250-380 ° C

Water feed rate: 4: 1 / total feed gas: water molar ratio / Catalyst particle size: 0.5-1.0 mm diameter

Catalyst assays are generally performed by first adjusting the proportion of feed materials and flow rates, then gradually increasing the temperature and monitoring the conversion and selectivity as the process progresses. With increasing temperature, the oxygen concentration slowly decreases (increasing ethane conversion / combustion), and when the oxygen is completely depleted, water is added to the reactor again to increase selectivity.

The results are shown in Table 1 below.

Table 1

Example Catalyst Bed temp. N Etánkonv. w Ethylene selectivity w Acetic acid selectivity to Acetic acid selectivity (with water supply) M 1 (III) 325 15 70 21 - 2 (ARC) 328 12 57 19 43 3 (V) 334 11 53 21 49 4 (VI) 332 6 53 28 37 5 (VII) 325 2 61 0 0

Catalyst test at higher pressure:

The catalyst test procedure described above is repeated, but in this experiment an excess pressure of 2.8 MPa is used. The catalyst used is a particulate catalyst of formula VIII having a diameter of 0.5 to 1.00 mm.

Water in the feed gas: 0.27 g / liter. The composition of the feed gas is 70% by volume ethane ·, 6.3% by volume oxygen, the remainder is helium. The results are shown in Table 2. The contact time is calculated by dividing the catalyst bed volume by the gas flow rate and then correcting for temperature and pressure.

Table 2

Test result for catalyst VIII

bed Temperature L C] Contact time H Ethane conversion H Acetic acid selectivity of ethylene 270 22 5.6 72.6 16.7 270 27 7.3 70.5 18.4 270 35 7.7 65.7 20.4 270 55 13.3 77.5 12.3 277 55 14.3 78.0 12.1 288 35 10.9 69.5 17.9 303 25 9.1 60.4 26.7 326 20 9.9 53.3 35.0 300 25 8.9 62.8 25.0 300 40 12.5 70.2 16.7

The catalysts (VIII) and (IX) are also tested. The catalysts have a particle diameter of 0.5-1.0 mm. The amount of water in the feed gas was 0.27 g / liter, and the pressure was 2.8 MPa. The composition of the feed gas is 70% by volume ethane, 6.3% by volume oxygen, the remainder is helium. The results obtained are shown in Table 3, which shows the change in selectivity with the change in the rhenium content of the catalyst.

Table 3

Catalyst Contact time M bed Temperature Etánkonverzió H Acetic acid selectivity to of ethylene w (VIII) 22 267 5.3 73.1 16.1 (IX) 22 267 4.98 48.0 39.8 (VIII) 20.7 303 8.17 61.1 27.2 (IX) 20.7 303 10.81 51.5 34.7 (VIII) 20.0 325 9.955 9.05 53.0 34.8 (IX) 20.0 325 46.1 42.2

Claims (14)

A process for the preparation of a product comprising ethylene and / or acetic acid from gaseous ethane and / or ethylene comprising contacting a gas mixture comprising ethane and / or ethylene and molecular oxygen with a catalyst which combines with A-, X- and Y- oxygen. contains elements - the ratio of grams of elements A, X and Y in the catalyst is a: b: c; and the component in the catalyst has the formula Mo _d Re _e Wf; chromium, manganese, niobium, tantalum, titanium, vanadium and / or tungsten; it is bismuth, cerium, cobalt, copper, iron, potassium, magnesium, nickel, phosphorus, lead, antimony, silicon, tin, thallium, and / or uranium; is 1; is 0-2; is 0-2; is 0 or greater; is greater than 0; and its value 0 or greater. 2. / The The process according to claim 1, wherein the gaseous ethane is ethylene and optionally acetic acid. 3. A process according to claim 1 or 2 wherein X is manganese, niobium vanadium and / or tungsten. Process according to any one of the preceding claims, characterized in that a catalyst is used in which Y is an antimony, cerium and / or uranium atom. 5. A process according to claim 1 or 2, wherein the catalyst comprises A, niobium, antimony and Z elements combined with oxygen; the ratio of grams of A, niobium, antimony and Z elements in the catalyst is a: b: c: g, respectively; and in the catalyst A and a, b and c have the same meanings as 1. as defined in claim 1; Z is at least one of calcium, ruthenium or gallium; and g is 0-2. 6. A process according to claim 1 or 2 wherein the catalyst comprises A, vanadium, niobium, antimony and Z elements combined with oxygen; the ratio of grams of A, vanadium, niobium, antimony and Z elements in the composition is a: h: b: c: g, respectively; and in the catalyst A and Z are as defined in claim 5; a, b, c and g are as defined in claim 5; and h is from 0 to 1.0. • · * 7. A process according to claim 1 or 2, wherein the catalysts have the following composition and elements in combination with oxygen: ^M, 0.56 ^Re o , □ 6 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 ^Mo 0.37 ^Re 0 25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 ^W, 0.37 ^Re o, 25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 ' ^M ° 0.24 ^Re 0 37 ^V 0.26 ^Nb 0.07 ^Sb 0.04 ^Ca 0.02 ^Re 0, live ^v 0, 26 ^Nb 0.07 ^Ca 0.02 ^Sb 0.04 obsession ^M, 0.52 ^Re o 1 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 Process according to any one of the preceding claims, characterized in that the gas containing ethane and / or ethylene and molecular oxygen is contacted with the catalyst in the presence of steam. 9. A catalyst composition comprising A, X and Z elements combined with oxygen; grams of elements A, X and Y are: a: b: c; in the composition, the component is represented by the formula Mo ^ Re ^ VJ ^; is selected from the group consisting of chromium, manganese, niobium, tantalum, titanium, vanadium and / or tungsten; is bismuth, cerium, cobalt, copper, iron, potassium, magnesium, nickel, phosphorus, lead, antimony, silicon, tin, thallium and / or uranium; - 23 is a value of 1; b is □ - 2; c is 0 to 2; d + e + f = a; d is 0 or more; e is greater than 0; and f is a number greater than or equal to 0. 10. The catalyst composition of claim 9, wherein the X component is manganese, niobium, vanadium and / or tungsten. 11. The catalyst composition according to claim 9, wherein the Y component is antimony, cerium and / or uranium. 12. / A catalyst composition comprising A, niobium, antimony and Z elements combined with oxygen; The grammes of the elements A, niobium, antimony and Z are a: b: c: g, respectively; and A and a, b and c are as defined in claim 9; Z is at least one component of calcium, ruthenium or gallium; and g is 0-2. r • · ·· · ·· ··· ·· * <· «· 13. / A catalyst composition comprising A, vanadium, niobium antimony and Z elements combined with oxygen; the ratio of A, vanadium, niobium, antimony and Z elements is a: h: b: c: g, respectively; and that A and Z are as defined in claim 12; a, b, c and g are as defined in claim 12; and h is from 0 to 1.0. 14. / Catalyst preparation, characterized in that it consists of elements combined with oxygen as follows: ^M, 0.56 ^Re 0.06 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 ' ^Mo 0.37 ^Re 0.25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 ' ^W, 0.37 ^Re 0.25 ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02 ' ^Mo 0.24 ^Re 0.37 ^V 0.26 ^Nb 0.07 ^Sb 0.04 Pa ^a 0.02 ' ^Re 0.61 ^V 0.26 ^Nb 0.07 ^Ca 0.02 ^Sb 0.04 obsession ^Mo 0.52 ^Re 0, l ^V 0.26 ^Nb 0.07 ^Sb 0.03 ^Ca 0.02.